Compound, photoresist composition comprising same, photoresist pattern comprising same, and method for manufacturing photoresist pattern

ABSTRACT

A compound represented by Chemical Formula 1, a photoresist composition comprising the same, a photoresist pattern comprising the same, and a method for preparing a photoresist pattern

This application is a 35 U.S.C. 371 National Phase Entry Applicationfrom PCT/KR2019/013365 filed on Oct. 11, 2019, designating the UnitedStates, which claims priority to and the benefits of Korean PatentApplication No. 10-2018-0120978, filed with the Korean IntellectualProperty Office on Oct. 11, 2018, the entire contents of which areincorporated herein by reference. The present specification relates to acompound, a photoresist composition comprising the same, a photoresistpattern comprising the same, and a method for preparing a photoresistpattern.

TECHNICAL FIELD Background of the Invention

A photoresist composition is used in, for example, a process of amicroelectronic device for manufacturing small electronic componentswhen manufacturing computer chips and integrated circuits. A process ofa microelectronic device using a substrate material such as asilicon-based wafer used for manufacturing an integrated circuit isgenerally as follows.

A photoresist layer of a thin coating film is formed on a substrateusing a photoresist composition or a photoresist film, and then theresult is baked to fix the coating film on the substrate. The coatingfilm fixed on the substrate is image-wise exposed to radiation. Theexposed coating film is treated with a developing solution, and bydissolving and removing the exposed area or the unexposed area of thephotoresist, a microelectronic device is formed.

High integration of a semiconductor has been advanced along with thedevelopment of photolithography technologies unmatched by otherpatterning techniques in terms of performance, reliability, and humanand physical infrastructures.

Particularly, as a shorter light source and a matching photochemicalreaction photoresist are used, the degree of device integration hasrapidly increased with the development of KrF excimer laser (248 nm) andArF laser (193 nm) lithography technologies using a high sensitivitychemical amplification-type photoresist.

Although 193i lithography technology has advanced to a level ofprogressing a process of manufacturing a device having a minimum linewidth of mid/late 10 nm through quadruple patterning, the process maynot be generally used due to very high process costs and limitedobtainable pattern shapes, and the resolution of 16 nm is recognized asa threshold. Extreme ultraviolet rays (EUV) have been predicted as anonly technology capable of several nm patterning so far, however, theresolution of 12 nm is recognized as a threshold as well in this casedue to an absence of a high resolution photoresist. In view of theabove, development of an extreme ultraviolet photoresist has beenrequired for high integration of a semiconductor, however, somematerials currently developed have problems to resolve such as improvingsensitivity decrease, resolution and line width roughness (LWR).

BRIEF SUMMARY OF THE INVENTION

The present specification provides a compound, a photoresist compositioncomprising the same, a photoresist pattern comprising the same, and amethod for preparing a photoresist pattern.

One embodiment of the present application provides a compoundrepresented by the following Chemical Formula 1.

In Chemical Formula 1,

R₁ and R₂ are the same as or different from each other, and eachindependently hydrogen; a halogen group; a nitrile group; a hydroxylgroup; an ester group; a substituted or unsubstituted alkyl group; asubstituted or unsubstituted aryl group; or a substituted orunsubstituted heteroaryl group,

R₃ to R₆ are the same as or different from each other, and eachindependently hydrogen; a substituted or unsubstituted alkyl group; asubstituted or unsubstituted cycloalkyl group; a substituted orunsubstituted alkoxy group; a substituted or unsubstituted silyl group;a substituted or unsubstituted boron group; a substituted orunsubstituted amine group; a substituted or unsubstituted arylphosphinegroup; a substituted or unsubstituted phosphine oxide group; asubstituted or unsubstituted aryl group; or a substituted orunsubstituted heteroaryl group, and

Ar₁ and Ar₂ are the same as or different from each other, and eachindependently hydrogen; a halogen group; a substituted or unsubstitutedalkyl group; or a substituted or unsubstituted aryl group.

Another embodiment of the present application provides a photoresistcomposition comprising a resin; the compound according to the presentapplication; a photoacid generator (PAG); an acid diffusion controlagent; and a quencher.

Another embodiment of the present application provides a photoresistpattern comprising the photoresist composition according to the presentapplication.

Lastly, one embodiment of the present application provides a method forpreparing a photoresist pattern, the method comprising forming aphotoresist layer by coating the photoresist composition of the presentapplication on a semiconductor substrate; selectively exposing thephotoresist layer; and developing the exposed photoresist layer.

Advantageous Effects

A compound according to one embodiment of the present application iscapable of, by comprising a structure of Chemical Formula 1, furtherenhancing contrast of an exposed portion and an unexposed portion in aphotoresist process afterward, and is also capable of improving linewidth roughness (LWR) without reducing sensitivity.

In addition, the compound according to one embodiment of the presentapplication comprises a photo-degradable base having the structure ofChemical Formula 1, and thereby has no sensitivity decrease caused by anincrease in the base concentration of a photoresist pattern comprisingthe same, and is also capable of resolving a compatibility problem bychanging substituents of Chemical Formula 1 depending on a resinincluded in a photoresist composition.

In addition, a photoresist composition comprising the compound accordingto the present application is capable of high resolution and freelyforming pattern shapes by comprising the compound.

THE DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, the present specification will be described in more detail.

In the present specification, a description of a certain part“including” certain constituents means capable of further comprisingother constituents, and does not exclude other constituents unlessparticularly stated on the contrary.

Embodiments of the present disclosure will be described in detail withreference to accompanying drawings so that those skilled in the art mayreadily implement the present disclosure. However, the presentdisclosure may be embodied in various different forms, and is notlimited to the embodiments described herein.

One embodiment of the present specification provides a compoundrepresented by the following Chemical Formula 1.

In Chemical Formula 1,

R₁ and R₂ are the same as or different from each other, and eachindependently hydrogen; a halogen group; a nitrile group; a hydroxylgroup; an ester group; a substituted or unsubstituted alkyl ft) group; asubstituted or unsubstituted aryl group; or a substituted orunsubstituted heteroaryl group,

R₃ to R₆ are the same as or different from each other, and eachindependently hydrogen; a substituted or unsubstituted alkyl group; asubstituted or unsubstituted cycloalkyl group; a substituted orunsubstituted alkoxy group; a substituted or unsubstituted silyl group;a substituted or unsubstituted boron group; a substituted orunsubstituted amine group; a substituted or unsubstituted arylphosphinegroup; a substituted or unsubstituted phosphine oxide group; asubstituted or unsubstituted aryl group; or a substituted orunsubstituted heteroaryl group, and

Ar₁ and Ar₂ are the same as or different from each other, and eachindependently hydrogen; a halogen group; a substituted or unsubstitutedalkyl group; or a substituted or unsubstituted aryl group.

The compound according to one embodiment of the present application iscapable of, by comprising the structure of Chemical Formula 1, furtherenhancing contrast of an exposed portion and an unexposed portion in aphotoresist process afterward, and is also capable of improving linewidth roughness (LWR) without reducing sensitivity.

In addition, the compound according to one embodiment of the presentapplication comprises a photo-degradable base having the structure ofChemical Formula 1, and thereby has no sensitivity decrease caused by anincrease in the base concentration of a photoresist pattern comprisingthe same, and is also capable of resolving a compatibility problem bychanging substituents of Chemical Formula 1 depending on a resinincluded in a photoresist composition.

Examples of substituents in the present specification are describedbelow, however, the substituents are not limited thereto.

The term “substitution” means a hydrogen atom bonding to a carbon atomof a compound is changed to another substituent, and the position ofsubstitution is not limited as long as it is a position at which thehydrogen atom is substituted, that is, a position at which a substituentcan substitute, and when two or more substituents substitute, the two ormore substituents may be the same as or different from each other.

In the present specification, the term “substituted or unsubstituted”means being substituted with one, two or more substituents selected fromthe group consisting of a halogen group; a nitrile group; an imidegroup; an amide group; a carbonyl group; an ester group; a hydroxylgroup; a carboxyl group (—COOH); a sulfonic acid group (—SO₃H); asubstituted or unsubstituted alkyl group; a substituted or unsubstitutedcycloalkyl group; a substituted or unsubstituted alkoxy group; asubstituted or unsubstituted silyl group; a substituted or unsubstitutedboron group; a substituted or unsubstituted amine group; a substitutedor unsubstituted arylphosphine group; a substituted or unsubstitutedphosphine oxide group; a substituted or unsubstituted aryl group; and asubstituted or unsubstituted heterocyclic group, or being substitutedwith a substituent linking two or more substituents among thesubstituents illustrated above, or having no substituents. For example,“a substituent linking two or more substituents” may comprise a biphenylgroup. In other words, a biphenyl group may be an aryl group, orinterpreted as a substituent linking two phenyl groups.

In the present specification,

means a site bonding to other substituents or bonding sites.

In the present specification, the halogen group may comprise fluorine,chlorine, bromine or iodine.

In the present specification, the number of carbon atoms of the imidegroup is not particularly limited, but is preferably from 1 to 30.Specifically, compounds having structures as below may be included,however, the imide group is not limited thereto.

In the present specification, in the amide group, the nitrogen of theamide group may be substituted with a linear, branched or cyclic alkylgroup having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbonatoms. Specifically, compounds having the following structural formulaemay be included, however, the amide group is not limited thereto.

In the present specification, the number of carbon atoms of the carbonylgroup is not particularly limited, but is preferably from 1 to 30.Specifically, compounds having structures as below may be included,however, the carbonyl group is not limited thereto.

In the present specification, the ester group may be an alkyl estergroup in which the oxygen of the ester group is substituted with alinear, branched or cyclic alkyl group having 1 to 25 carbon atoms; acycloalkyl ester group in which the oxygen of the ester group issubstituted with a monocyclic or polycyclic cycloalkyl group having 3 to30 carbon atoms; or an aryl ester group in which the oxygen of the estergroup is substituted with an aryl group having 6 to 30 carbon atoms.Specifically, compounds having the following structural formulae may beincluded, however, the ester group is not limited thereto.

In the present specification, the alkyl group may be linear or branched,and although not particularly limited thereto, the number of carbonatoms is preferably from 1 to 30. Specific examples thereof may comprisemethyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl,tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl,isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl,2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl,heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl,octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl,2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl,1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl,5-methylhexyl and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularlylimited, but preferably has 3 to 30 carbon atoms. Specific examplesthereof may comprise cyclopropyl, cyclobutyl, cyclopentyl,3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl,3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl,3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl,cyclooctyl and the like, but are not limited thereto.

In the present specification, the alkoxy group may be linear, branchedor cyclic. The number of carbon atoms of the alkoxy group is notparticularly limited, but is preferably from 1 to 30. Specific examplesthereof may comprise methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy,isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy,n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and thelike, but are not limited thereto.

In the present specification, the amine group may be selected from thegroup consisting of —NH₂; a monoalkylamine group; a dialkylamine group;an N-alkylarylamine group; a monoarylamine group; a diarylamine group;an N-arylheteroarylamine group; an N-alkylheteroarylamine group, amonoheteroarylamine group and a diheteroarylamine group, and althoughnot particularly limited thereto, the number of carbon atoms ispreferably from 1 to 30. Specific examples of the amine group maycomprise a methylamine group, a dimethylamine group, an ethylaminegroup, a diethylamine group, a phenylamine group, a naphthylamine group,a biphenylamine group, an anthracenylamine group, a9-methyl-anthracenylamine group, a diphenylamine group, a ditolylaminegroup, an N-phenyltolylamine group, a triphenylamine group, anN-phenylbiphenylamine group; an N-phenylnaphthylamine group; anN-biphenylnaphthylamine group; an N-naphthylfluorenylamine group; anN-phenylphenanthrenylamine group; an N-biphenylphenanthrenylamine group;an N-phenylfluorenylamine group; an N-phenylterphenylamine group; anN-phenanthrenylfluorenylamine group; an N-biphenylfluorenylamine groupand the like, but are not limited thereto.

In the present specification, the N-alkylarylamine group means an aminegroup in which N of the amine group is substituted with an alkyl groupand an aryl group.

In the present specification, the N-arylheteroarylamine group means anamine group in which N of the amine group is substituted with an arylgroup and a heteroaryl group.

In the present specification, the N-alkylheteroarylamine group means anamine group in which N of the amine group is substituted with an alkylgroup and a heteroaryl group.

In the present specification, the alkyl group in the monoalkylaminegroup, the dialkylamine group, the N-alkylarylamine group, thealkylthioxy group, the alkylsulfoxy group and the N-alkylheteroarylaminegroup is the same as the examples of the alkyl group described above.Specifically, the alkylthioxy group may comprise a methylthioxy group,an ethylthioxy group, a tert-butylthioxy group, a hexylthioxy group, anoctylthioxy group and the like, and the alkylsulfoxy group may comprisemesyl, an ethylsulfoxy group, a propylsulfoxy group, a butylsulfoxygroup and the like, however, the alkylthoixy group and the alkylsulfoxygroup are not limited thereto.

In the present specification, specific examples of the silyl group maycomprise a trimethylsilyl group, a triethylsilyl group, at-butyldimethylsilyl group, a vinyldimethylsilyl group, apropyldimethylsilyl group, a triphenylsilyl group, a diphenylsilylgroup, a phenylsilyl group and the like, but are not limited thereto.

In the present specification, the boron group may be —BR₁₀₀R₁₀₁. R₁₀₀and R₁₀₁ are the same as or different from each other, and may be eachindependently selected from the group consisting of hydrogen; deuterium;halogen; a nitrile group; a substituted or unsubstituted monocyclic orpolycyclic cycloalkyl group having 3 to 30 carbon atoms; a substitutedor unsubstituted linear or branched alkyl group having 1 to 30 carbonatoms; a substituted or unsubstituted monocyclic or polycyclic arylgroup having 6 to 30 carbon atoms; and a substituted or unsubstitutedmonocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

In the present specification, specific examples of the phosphine oxidegroup may comprise a diphenylphosphine oxide group, adinaphthylphosphine oxide group and the like, but are not limitedthereto.

In the present specification, the aryl group is not particularlylimited, but preferably has 6 to 30 carbon atoms, and the aryl group maybe monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbonatoms is not particularly limited, but is preferably from 6 to 30.Specific examples of the monocyclic aryl group may comprise a phenylgroup, a biphenyl group, a terphenyl group and the like, but are notlimited thereto.

When the aryl group is a polycyclic aryl group, the number of carbonatoms is not particularly limited, but is preferably from 10 to 30.Specific examples of the polycyclic aryl group may comprise a naphthylgroup, an anthracenyl group, a phenanthryl group, a triphenyl group, apyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl groupand the like, but are not limited thereto.

In the present specification, the fluorenyl group may be substituted,and adjacent groups may bond to each other to form a ring.

When the fluorenyl group is substituted, the following structures may beincluded, however, the structure is not limited thereto.

In the present specification, the “adjacent” group may mean asubstituent substituting an atom directly linked to an atom substitutedby the corresponding substituent, a substituent sterically most closelypositioned to the corresponding substituent, or another substituentsubstituting an atom substituted by the corresponding substituent. Forexample, two substituents substituting ortho positions in a benzenering, and two substituents substituting the same carbon in an aliphaticring may be interpreted as groups “adjacent” to each other.

In the present specification, the aryl group in the monoarylamine group,the diarylamine group, the aryloxy group, the arylthioxy group, thearylsulfoxy group, the N-arylalkylamine group, the N-arylheteroarylaminegroup and the arylphosphine group is the same as the examples of thearyl group described above. Specific examples of the aryloxy group maycomprise a phenoxy group, a p-tolyloxy group, an m-tolyloxy group, a3,5-dimethyl-phenoxy group, a 2,4,6-trimethylphenoxy group, ap-tert-butylphenoxy group, a 3-biphenyloxy group, a 4-biphenyloxy group,a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methyl-1-naphthyloxygroup, a 5-methyl-2-naphthyloxy group, a 1-anthryloxy group, a2-anthryloxy group, a 9-anthryloxy group, a 1-phenanthryloxy group, a3-phenanthryloxy group, a 9-phenanthryloxy group and the like. Specificexamples of the arylthioxy group may comprise a phenylthioxy group, a2-methylphenylthioxy group, a 4-tert-butylphenylthioxy group and thelike, and specific examples of the arylsulfoxy group may comprise abenzenesulfoxy group, a p-toluenesulfoxy group and the like. However,the aryloxy group, the arylthioxy group and the arylsulfoxy group arenot limited thereto.

In the present specification, the heteroaryl group is a group comprisingone or more atoms that are not carbon, that is, heteroatoms, andspecifically, the heteroatom may comprise one or more atoms selectedfrom the group consisting of O, N, Se, S and the like. The number ofcarbon atoms is not particularly limited, but is preferably from 2 to30, and the heteroaryl group may be monocyclic or polycyclic. Examplesof the heterocyclic group may comprise a thiophene group, a furanylgroup, a pyrrole group, an imidazolyl group, a thiazolyl group, anoxazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, atriazinyl group, a triazolyl group, an acridyl group, a pyridazinylgroup, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, aquinoxalinyl group, a phthalazinyl group, a pyridopyrimidyl group, apyridopyrazinyl group, a pyrazinopyrazinyl group, an isoquinolinylgroup, an indolyl group, a carbazolyl group, a benzoxazolyl group, abenzimidazolyl group, a benzocarbazolyl group, a benzothiophene group, adibenzothiophene group, a benzofuranyl group, a phenanthrolinyl group,an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, abenzothiazolyl group, a phenothiazinyl group, a dibenzofuranyl group andthe like, but are not limited thereto.

In the present specification, examples of the heteroaryl group in themonoheteroarylamine group, the diheteroarylamine group, theN-arylheteroarylamine group and the N-alkylheteroarylamine group are thesame as the examples of the heteroaryl group described above.

In the present specification, the hydrocarbon ring may be aromatic,aliphatic or a fused ring of aromatic and aliphatic, and may be selectedfrom among the examples of the cycloalkyl group or the aryl group exceptfor those that are not monovalent.

In the present specification, the aromatic hydrocarbon ring may bemonocyclic or polycyclic, and may be selected from among the examples ofthe aryl group except for those that are not monovalent.

In the present specification, the heteroring comprises one or more atomsthat are not carbon, that is, heteroatoms, and specifically, theheteroatom may comprise one or more atoms selected from the groupconsisting of O, N, Se, S and the like. The heteroring may be monocyclicor polycyclic, may be aromatic, aliphatic or a fused ring of aromaticand aliphatic, and may be selected from among the examples of theheteroaryl group except for those that are not monovalent.

In one embodiment of the present application, R₁ and R₂ are the same asor different from each other, and may be each independently hydrogen; ahalogen group; a nitrile group; a hydroxyl group; an ester group; asubstituted or unsubstituted alkyl group; a substituted or unsubstitutedaryl group; or a substituted or unsubstituted heteroaryl group.

In another embodiment, R₁ and R₂ are the same as or different from eachother, and may be each independently hydrogen; a halogen group; an estergroup; a substituted or unsubstituted C₁ to C₆₀ alkyl group; asubstituted or unsubstituted C₆ to C₆₀ aryl group; or a substituted orunsubstituted C₂ to C₆₀ heteroaryl group.

In another embodiment, R₁ and R₂ are the same as or different from eachother, and may be each independently hydrogen; a halogen group; an estergroup; a substituted or unsubstituted C₁ to C₄₀ alkyl group; asubstituted or unsubstituted C₆ to C₄₀ aryl group; or a C₂ to C₄₀heteroaryl group.

In another embodiment, R₁ and R₂ are the same as or different from eachother, and may be each independently hydrogen; a halogen group; an estergroup; a C₁ to C₄₀ alkyl group unsubstituted or substituted with ahalogen group; a C₆ to C₄₀ aryl group unsubstituted or substituted withone or more substituents selected from the group consisting of ahaloalkyl group, a halogen group and an alkyl ester group; or a C₂ toC₄₀ heteroaryl group.

In another embodiment, R₁ and R₂ are the same as or different from eachother, and may be each independently hydrogen; a halogen group; an estergroup; a C₁ to C₄₀ alkyl group unsubstituted or substituted with ahalogen group; a C₆ to C₄₀ aryl group unsubstituted or substituted witha haloalkyl group, a halogen group and a methyl ester group; or a C₂ toC₄₀ heteroaryl group.

In another embodiment, R₁ and R₂ are the same as or different from eachother, and may be each independently hydrogen; a C₁ to C₄₀ alkyl group;a C₆ to C₄₀ aryl group unsubstituted or substituted with a methyl estergroup; or a substituted or unsubstituted C₂ to C₄₀ N-containingheteroaryl group.

In another embodiment, R₁ and R₂ are the same as or different from eachother, and may be each independently hydrogen; a methyl group; atrifluoromethyl group; a pyridine group; a pyrimidine group; or a phenylgroup unsubstituted or substituted with one or more substituentsselected from the group consisting of a trifluoromethyl group, a halogengroup and a methyl ester group.

In another embodiment, R₁ and R₂ may be any one selected from among thefollowing structural formulae

In the structural formulae,

R is hydrogen; a substituted or unsubstituted alkyl group; a substitutedor unsubstituted aryl group; or a substituted or unsubstitutedheteroaryl group.

In the structural formulae,

means a site linked to substituents.

By R₁ and R₂ having the above-mentioned substituents, high compatibilitymay be obtained depending on the type of a resin included in aphotoresist composition afterward.

In one embodiment of the present application, R₃ may be a substituted orunsubstituted C₁ to C₆₀ alkyl group.

In another embodiment, R₃ may be a substituted or unsubstituted C₁ toC₃₀ alkyl group.

In another embodiment, R₃ may be a C₁ to C₃₀ alkyl group.

In another embodiment, R₃ may be a methyl group.

In one embodiment of the present application, R₄ to R₆ are the same asor different from each other, and may be each independently asubstituted or unsubstituted C₆ to C₆₀ aryl group.

In another embodiment, R₄ to R₆ are the same as or different from eachother, and may be each independently a substituted or unsubstituted C₆to C₄₀ aryl group.

In another embodiment, R₄ to R₆ are the same as or different from eachother, and may be each independently a C₆ to C₄₀ aryl group.

In another embodiment, R₁ to R₆ may be a phenyl group.

In one embodiment of the present application, Ar₁ and Ar₂ are the sameas or different from each other, and may be each independently hydrogen;or a halogen group, and at least one of Ar₁ and Ar₂ may comprise ahalogen group.

In another embodiment, Ar₁ and Ar₂ are the same as or different fromeach other, and may be each independently hydrogen; or a fluoro group,and at least one of Ar₁ and Ar₂ may comprise a fluoro group.

In the compound provided in one embodiment of the present application,the compound represented by Chemical Formula 1 is any one of thefollowing compounds.

One embodiment of the present application provides a photoresistcomposition comprising a resin; the compound according to the presentapplication; a photoacid generator (PAG); an acid diffusion controlagent; and a quencher.

The photoresist composition comprising the compound according to thepresent application is capable of high resolution and freely formingpattern shapes by comprising the compound.

Particularly, the photoresist composition according to the presentapplication comprises the compound of Chemical Formula 1 as aphoto-degradable base, and is thereby capable of further enhancingcontrast of an exposed portion and an unexposed portion, and is capableof improving line width roughness (LWR) without reducing sensitivity.

The photoresist composition is used for, for example, forming a micro ornanopattern used in a process for manufacturing a microelectronic deviceto manufacture small electronic components when manufacturing computerchips and integrated circuits, and such a pattern-forming process isreferred to as a lithography process. A lithography process using asubstrate material such as a silicon-based wafer used for manufacturingan integrated circuit is generally as follows.

A thin photoresist layer is formed on a substrate using a photoresistcomposition coating film or a photoresist film, and then the result isbaked to fix the photoresist layer on the substrate. The photoresistlayer fixed on the substrate is image-wise exposed to radiation. Theexposed photoresist layer is treated with a developing solution, and bydissolving and removing the exposed area of the photoresist layer, amicro or nanopattern is formed.

In one embodiment of the present application, the resin may comprise oneor more selected from the group consisting of a (meth)acrylate-basedresin; a norbornene resin; a styrene-based resin; and an epoxy resin.

In one embodiment of the present application, the resin comprises one ormore monomers selected from among monomers represented by the followingChemical Formulae 2 and 3.

In Chemical Formulae 2 and 3,

R₁₁ is hydrogen; a halogen group; a substituted or unsubstituted alkylgroup; a substituted or unsubstituted aryl group; or a substituted orunsubstituted heteroaryl group,

P is hydrogen; a halogen group; a nitrile group; a hydroxyl group; asubstituted or unsubstituted ester group; a substituted or unsubstitutedalkyl group; a substituted or unsubstituted cycloalkyl group; asubstituted or unsubstituted alkoxy group; a substituted orunsubstituted silyl group; a substituted or unsubstituted boron group; asubstituted or unsubstituted amine group; a substituted or unsubstitutedarylphosphine group; a substituted or unsubstituted phosphine oxidegroup; a substituted or unsubstituted aryl group; or a substituted orunsubstituted heteroaryl group, and

m and n are each an integer of 1 to 100.

In one embodiment of the present application, the resin comprises one ormore monomers selected from among monomers represented by the followingChemical Formulae 2-1 and 3-1.

In Chemical Formulae 2-1 and 3-1,

L is a direct bond; a substituted or unsubstituted alkylene group; asubstituted or unsubstituted arylene group; or a substituted orunsubstituted heteroarylene group,

R₁₁ is hydrogen; a halogen group; a substituted or unsubstituted alkylgroup; a substituted or unsubstituted aryl group; or a substituted orunsubstituted heteroaryl group,

R₁₂ is hydrogen; a halogen group; a hydroxyl group; a substituted orunsubstituted alkyl group; a substituted or unsubstituted cycloalkylgroup; a substituted or unsubstituted aryl group; or a substituted orunsubstituted heteroaryl group, and

m and n are each an integer of 1 to 100.

In one embodiment of the present application, L may be a direct bond.

In one embodiment of the present application, R₁₁ may be hydrogen; or asubstituted or unsubstituted alkyl group.

In another embodiment, R₁₁ may be a substituted or unsubstituted C1 toC60 alkyl group.

In another embodiment, R₁₁ may be a substituted or unsubstituted C1 toC40 alkyl group.

In another embodiment, R₁₁ may be a linear C1 to C40 alkyl group.

In another embodiment, R₁₁ may be a methyl group.

In one embodiment of the present application, R₁₂ may be any oneselected from among the following structural formulae

In the structural formulae,

means a site linked to O of Chemical Formula 2-1 or 3-1.

In one embodiment of the present application, the resin may have aweight average molecular weight of greater than or equal to 3000 g/moland less than or equal to 15000 g/mol, and preferably greater than orequal to 3500 g/mol and less than or equal to 13000 g/mol.

By the weight average molecular weight of the resin satisfying theabove-mentioned range, a photoresist pattern formed afterward hasexcellent sensitivity, and has no cracks formed thereon.

The weight average molecular weight is one of average molecular weightsin which molecular weights are not uniform and a molecular weight of acertain polymer material is used as a base, and is a value obtained byaveraging molecular weights of component molecular species of a polymercompound having molecular weight distribution by a weight fraction.

The weight average molecular weight may be measured through a gelpermeation chromatography (GPC) analysis.

The resin is a polymer dissociated by an acid and thereby havingincreased solubility for an alkali developing solution, and due to astructure of the polymer main chain, a glass transition temperature isvery high suppressing acid diffusion, and as a result, high resolutionis obtained.

In one embodiment of the present application, the photoacid generator isa material generating an acid by receiving light, and is a materialincreasing solubility by having an unstable group of a resin to react,and enabling patterning of a photoresist pattern comprising the sameafterward.

The photoacid generator is preferably a salt of a cation and an anion.The photoacid generator preferably has sufficiently low radiationabsorption at the wavelength of exposure, and does not directly generatean acid with respect to radiation at the time of exposure. As a result,in the photoresist composition, an acid may be generated by aphotosensitive reaction only in an exposed portion of a pattern duringexposure.

The photoacid generator may specifically comprise an onium saltcompound, a diazomethane compound, a sulfonimide compound and the like.Examples of the onium salt compound may comprise a sulfonium saltcompound, a tetrahydrothiophenium salt compound, an iodonium saltcompound and the like. The photoacid generator preferably comprises atleast one type selected from the group consisting of an sulfonium saltcompound, an iodonium salt compound, sulfonyl diazomethane, N-sulfonyloxyimide and oxime-O-sulfonate type photoacid generators, and morepreferably comprises at least one type of compound selected from thegroup consisting of a sulfonium salt compound and an iodonium saltcompound.

In one embodiment of the present application, specific examples of thesulfonium salt compound may comprise triphenylsulfoniumtrifluoromethanesulfonate, triphenylsulfoniumnonafluoro-n-butanesulfonate, triphenylsulfoniumperfluoro-n-octanesulfonate, triphenylsulfonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate,4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate,4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate,4-cyclohexylphenyldiphenylsulfonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate,4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate,4-methanesulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate,4-methanesulfonylphenyldiphenylsulfonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate and thelike.

Specific examples of the iodonium salt compound may comprisediphenyliodonium trifluoromethanesulfonate, diphenyliodoniumnonafluoro-n-butanesulfonate, diphenyliodoniumperfluoro-n-octanesulfonate, diphenyliodonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate,bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate,bis(4-t-butylphenyl)iodonium perfluoro-n-octanesulfonate,bis(4-t-butylphenyl)iodonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate and thelike.

In one embodiment of the present application, the photoacid generatormay be represented by the following Chemical Formula 4.

In Chemical Formula 4,

L₁₁ is a direct bond; a substituted or unsubstituted alkylene group; asubstituted or unsubstituted arylene group; or a substituted orunsubstituted heteroarylene group, s is an integer of 1 to 5, and when sis 2 or greater, L₁₁s are the same as or different from each other,

Q⁺ is an onium cation,

X⁻ is an acid anion, and

R₂₁ is hydrogen; a substituted or unsubstituted alkyl group; asubstituted or unsubstituted cycloalkyl group; a substituted orunsubstituted aryl group; or a substituted or unsubstituted heteroarylgroup.

In one embodiment of the present application, X⁻ is an acid anion, andthe acid anion may be one type of anion group selected from the groupconsisting of a sulfonic acid anion, a carboxylic acid anion, asulfonylimide anion, a bis(alkylsulfonyl)imide anion and atris(alkylsulfonyl)methide anion.

In one embodiment of the present application, X⁻ may be —SO₃ ⁻.

In one embodiment of the present application, Q⁺ may be an onium cation.

The onium cation may be an onium cation comprising an S; I; O; N; P; Cl;Br; F; As; Se; Sn; Sb; Te; or Bi element.

In another embodiment, Q⁺ may be represented by the following ChemicalFormula 4-1.

In Chemical Formula 4-1,

R₂₂ to R₂₄ are a substituted or unsubstituted aryl group; or asubstituted or unsubstituted heteroaryl group.

In one embodiment of the present application, L₁₁ may be a direct bond;a substituted or unsubstituted alkylene group; a substituted orunsubstituted arylene group; or a substituted or unsubstitutedheteroarylene group.

In another embodiment, L₁₁ may be a direct bond; a substituted orunsubstituted C1 to C60 alkylene group; a substituted or unsubstitutedC6 to C60 arylene group; or a substituted or unsubstituted C2 to C60heteroarylene group.

In another embodiment, L₁₁ may be a direct bond; or a substituted orunsubstituted C1 to C60 alkylene group.

In another embodiment, L₁₁ may be a direct bond; or a C1 to C60 alkylenegroup unsubstituted or substituted with a halogen group.

In another embodiment, L₁₁ may be a direct bond; or a C1 to C40 alkylenegroup unsubstituted or substituted with a halogen group.

In another embodiment, L₁₁ may be a direct bond; or a C1 to C40 alkylenegroup unsubstituted or substituted with a fluoro group (—F).

In another embodiment, L₁₁ may be a direct bond; or a methylene groupunsubstituted or substituted with a fluoro group (—F).

In one embodiment of the present application, R₂₂ to R₂₄ may be asubstituted or unsubstituted C6 to C60 aryl group.

In another embodiment, R₂₂ to R₂₄ may be a C6 to C60 aryl groupunsubstituted or substituted with a C1 to C60 alkyl group.

In another embodiment, R₂₂ to R₂₄ may be a C6 to C40 aryl groupunsubstituted or substituted with a C1 to C40 alkyl group.

In another embodiment, R₂₂ to R₂₄ may be a phenyl group unsubstituted orsubstituted with a tert-butyl group.

In one embodiment of the present application, R₂₁ may be a substitutedor unsubstituted alkyl group; or a substituted or unsubstitutedcycloalkyl group.

In another embodiment, R₂₁ may be a substituted or unsubstituted C1 toC60 alkyl group; or a substituted or unsubstituted C3 to C60 cycloalkylgroup.

In one embodiment of the present application, the photoacid generatormay be represented by the following structure.

In one embodiment of the present application, the acid diffusion controlagent and the quencher are materials suppressing a reaction in anunexposed portion caused by an acid generated in the exposed portiondiffusing to the unexposed portion.

In one embodiment of the present application, the acid diffusion controlagent and the quencher may be represented by the following ChemicalFormula 5.

In Chemical Formula 5,

R₃₁ to R₃₃ are selected from the group consisting of a substituted orunsubstituted alkyl group; and a substituted or unsubstituted an estergroup, or adjacent two or more groups bond to form a substituted orunsubstituted aliphatic hydrocarbon ring or a substituted orunsubstituted heteroring.

In one embodiment of the present application, the acid diffusion controlagent and the quencher may be any one selected from among the followingstructural formulae.

In one embodiment of the present application, the photoresistcomposition may further comprise a solvent, and the solvent may be oneor more types selected from the group consisting of acetone, methylethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethylcellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethylether, ethylene glycol diethyl ether, propylene glycol dimethyl ether,propylene glycol diethyl ether, diethylene glycol dimethyl ether,diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether,chloroform, methylene chloride, 1,2-dichloroethane,1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethene,hexane, heptane, octane, cyclohexane, benzene, toluene, xylene,methanol, ethanol, isopropanol, propanol, butanol, t-butanol,2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone,cyclopentanone, propylene glycol methyl ether acetate, propylene glycolethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate,ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate,propylene glycol monomethyl ether and dipropylene glycol monomethylether, but is not limited thereto.

As the solvent, propylene glycol methyl ether acetate (PGMEA) may bepreferably used.

In one embodiment of the present application, the photoresistcomposition may further comprise one or more selected from the groupconsisting of a surfactant; a photosensitizer; and a photobasegenerator.

In one embodiment of the present application, the surfactant may be usedwithout limit as long as it is a material performing a role ofsuppressing bubble generation in the photoresist composition, enhancingadhesive strength, and increasing coating uniformity.

In one embodiment of the present application, the photosensitizer is amaterial increasing activity of the photoacid generator, and is amaterial performing a role of increasing photoresist patternsensitivity.

In one embodiment of the present application, the photobase generatormay be used without limit as long as it is a material generating a baseby receiving light.

In the photoresist composition provided in one embodiment of the presentapplication, the photoresist composition comprises the compound ingreater than or equal to 0.1 parts by weight and less than or equal to20 parts by weight based on 100 parts by weight of the resin.

In another embodiment, the photoresist composition may comprise thecompound in greater than or equal to 0.1 parts by weight and less thanor equal to 20 parts by weight, preferably in greater than or equal to0.1 parts by weight and less than or equal to 15 parts by weight, andmore preferably in greater than or equal to 0.2 parts by weight and lessthan or equal to 10 parts by weight based on 100 parts by weight of theresin.

In the photoresist composition provided in one embodiment of the presentapplication, the photoresist composition comprises the photoacidgenerator in greater than or equal to 0.1 parts by weight and less thanor equal to 20 parts by weight based on 100 parts by weight of theresin.

In another embodiment, the photoresist composition may comprise thephotoacid generator in greater than or equal to 0.1 parts by weight andless than or equal to 20 parts by weight, preferably in greater than orequal to 1 parts by weight and less than or equal to 15 parts by weight,and more preferably in greater than or equal to 2 parts by weight andless than or equal to 10 parts by weight based on 100 parts by weight ofthe resin.

In the photoresist composition provided in one embodiment of the presentapplication, the photoresist composition comprises the acid diffusioncontrol agent in greater than or equal to 0.1 parts by weight and lessthan or equal to 20 parts by weight based on 100 parts by weight of theresin.

In another embodiment, the photoresist composition may comprise the aciddiffusion control agent in greater than or equal to 0.1 parts by weightand less than or equal to 20 parts by weight, preferably in greater thanor equal to 0.3 parts by weight and less than or equal to 10 parts byweight, and more preferably in greater than or equal to 0.5 parts byweight and less than or equal to 5 parts by weight based on 100 parts byweight of the resin.

In one embodiment of the present application, the photoresistcomposition may comprise the surfactant in greater than or equal to 0.01parts by weight and less than or equal to 5 parts by weight based on 100parts by weight of the resin.

In one embodiment of the present application, the photoresistcomposition may comprise the photosensitizer in greater than or equal to0.1 parts by weight and less than or equal to 10 parts by weight basedon 100 parts by weight of the resin.

In one embodiment of the present application, the photoresistcomposition may comprise the photobase generator in greater than orequal to 0.1 parts by weight and less than or equal to 10 parts byweight based on 100 parts by weight of the resin.

In the photoresist composition provided in one embodiment of the presentapplication, the photoresist composition comprises the quencher ingreater than or equal to 0.1 parts by weight and less than or equal to10 parts by weight based on 100 parts by weight of the resin.

In another embodiment, the photoresist composition may comprise thequencher in greater than or equal to 0.1 parts by weight and less thanor equal to 10 parts by weight, preferably in greater than or equal to0.1 parts by weight and less than or equal to 5 parts by weight, andmore preferably in greater than or equal to 0.2 parts by weight and lessthan or equal to 1 parts by weight based on 100 parts by weight of theresin.

By comprising the materials in the above-mentioned weight ranges, thephotoresist composition is capable of obtaining high resolution andfreely forming pattern shapes.

One embodiment of the present specification provides a photoresistpattern comprising the photoresist composition according to oneembodiment of the present application.

In one embodiment of the present application, the photoresistcomposition may be included in the photoresist pattern as it is.

One embodiment of the present application provides a photoresist patternformed using the photoresist composition.

In one embodiment of the present application, the photoresist patternmay be formed using the following preparation method.

In one embodiment of the present specification, a photolithographyprocess forming a photoresist pattern using the photoresist compositionmay comprise forming a photoresist layer on a semiconductor substrateusing the photoresist composition; selectively exposing the photoresistlayer; and developing the exposed photoresist layer.

One embodiment of the present application provides a method forpreparing a photoresist pattern, the method comprising forming aphotoresist layer by coating a photoresist composition on asemiconductor substrate; selectively exposing the photoresist layer; anddeveloping the exposed photoresist layer.

In one embodiment of the present application, the forming of aphotoresist layer comprises coating a photoresist composition on asubstrate; and drying (soft baking) the coated material.

In one embodiment of the present specification, as the method of coatingthe photoresist composition, a method of coating with a spin coater, abar coater, a blade coater, a curtain coater, a screen printer or thelike, a method of spraying with a spray coater, or the like, may beused, however methods capable of coating a photoresist composition maybe used without limit.

In the drying (soft baking) of the coated material, the coated materialmay be dried under a condition of 30 seconds to 120 seconds at 70° C. to180° C. The drying method may comprise, for example, an oven, a hotplate, vacuum drying and the like, but is not limited thereto. Whengoing through the drying, a solvent is removed from the photoresistcomposition increasing adhesive strength between the wafer and thephotosensitive resin layer, and the photoresist layer may be formed onthe semiconductor substrate.

In one embodiment of the present application, the selectively exposingof the photoresist layer is aligning a mask on the photoresist, andexposing an area of the photoresist layer not covered by the mask toultraviolet rays. The mask may be in contact with the photoresist layer,or may also be aligned at a certain distance from the photoresist layer.

In the exposure process, a light source irradiated as a lightirradiation means may comprise electromagnetic waves, extremeultraviolet rays (EUV), from ultraviolet rays to visible rays, anelectron beam, X-rays, laser rays and the like. In addition, as a methodof irradiating the light source, known means such as a high pressuremercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a coldcathode tube for a copier, an LED and a semiconductor laser may be used.

In one embodiment of the present application, the selectively exposingof the photoresist layer may further comprise heating (post-exposurebaking) the exposed photoresist layer after the exposure. By heating theexposed photoresist layer, components in the photoresist composition arerealigned, reducing a standing wave of the photoresist layer.

The heating (post-exposure baking) of the photoresist layer may beconducted under a condition of 30 seconds to 120 seconds at 70° C. to180° C.

In one embodiment of the present application, the developing of theexposed photoresist layer is removing the exposed portion in thephotoresist layer by immersing in a developing solution. As thedeveloping method, photoresist developing methods known in the art suchas a rotary spray method, a paddle method or an immersion methodaccompanying ultrasonic treatment may be used, however, the method isnot limited thereto.

Examples of the developing solution may comprise alkali metal oralkaline earth metal hydroxides, carbonates, hydrogen carbonates, anaqueous basic solution such as an ammonia water quaternary ammonium saltmay be used. Among these, an aqueous ammonia quaternary ammoniumsolution such as an aqueous tetramethyl ammonium solution isparticularly preferred.

Through steps as above, the photoresist pattern according to oneembodiment of the present application may be formed.

In one embodiment of the present disclosure, the method for forming apattern of a photoresist layer may be used in a semiconductormanufacturing process.

Specifically, in one embodiment of the semiconductor manufacturingprocess, a process of etching an area of the semiconductor substrate notcovered by the photoresist layer, and removing (ashing) the photoresistlayer from the semiconductor substrate is further included in thephotolithography process.

The etching of an area of the semiconductor substrate not covered by thephotoresist layer is etching the semiconductor substrate area other thanthe pattern of the photoresist layer.

The removing of the photoresist layer from the semiconductor substratemay use known methods, and for example, may be conducted by heating awafer in a low pressure state using a reaction chamber, and theninjecting a plasma comprising an oxygen group or an oxygen ion thereto.

The semiconductor substrate is not limited, and those known in the artmay be used. For example, substrates for electronic components, or thosehaving a predetermined wiring pattern formed to thereon may be includedas an example. Examples of the substrate for an electronic component maycomprise substrates made of metal or glass substrates such as silicon,silicon nitride, titanium, tantalum, palladium, titanium tungsten,copper, chromium, iron, aluminum, gold and nickel, or the like. Examplesof the wiring pattern material may comprise copper, solder, chromium,aluminum, nickel, gold and the like, but are not limited thereto.

One embodiment of the present specification provides an electronicdevice comprising the photoresist pattern.

The electronic device may be used without limit as long as it is capableof using a photoresist layer prepared from the composition according tothe present specification. For example, it may be used in a wide rangeof applications such as circuit substrate manufacturing, electroniccomponent manufacturing, connection terminals such as bumps or metalposts, and wiring patterns.

Hereinafter, the present specification will be described in detail withreference to examples in order to specifically describe the presentspecification. However, the examples according to the presentspecification may be modified to various other forms, and the scope ofthe present specification is not to be construed as being limited to theexamples described below. Examples of the present specification areprovided in order to more fully describe the present specification tothose having average knowledge in the art.

PREPARATION EXAMPLE Synthesis of Compounds

In the syntheses of the compounds, the compounds were synthesized usingsubstituents described in the following Table 1.

TABLE 1 R₁ R₂ Yield (%) Preparation Example 1 H H 95 Preparation Example2 CH₃ H 93 Preparation Example 3 Ph H 94 Preparation Example 4 CH₃ CH₃93 Preparation Example 5 CH₃ 4-CO₂CH₃P—C₆H₄ 90 Preparation Example 6 Ph2-Pyridinyl 91

Preparation of Intermediate 1

Cyclopentadiene (132.2 g, 2.0 mol), 2-carboxyethyl acrylate (130.1 g,1.0 mol) and 4-methoxyphenol (2.4 g, 0.02 mol) were introduced to a highpressure reactor, and the result was reacted for 18 hours at 180° C.,and then vacuum distilled to obtain Intermediate 1 (190 g, 97%). 1H-NMR(CDCl3): (ppm) δ=6.3 (dd, H), 6.2 (dd, H), 3.6 (s, 3H), 3.34 (dd, H),3.29 (dd, H), 3.2-3.1 (m, 2H), 1.5 (m, H), 1.4-1.3 (br, H)

Preparation of Intermediate 2

Intermediate 1 (196 g, 1.0 mol), sodium1,1-difluoro-2-hydroxyethane-1-sulfonate (220.9 g, 1.2 mol) and H₂SO₄(19.6 g, 0.2 mol) were introduced and reacted for 6 hours at 60° C.After the reaction was finished, H₂O (1 L) was introduced thereto, theresult was extracted 3 times with ethyl acetate (1 L), and the solventwas removed. The obtained result was recrystallized with EtOH to obtainIntermediate 2 (330 g, 91%).

1H-NMR (DMSO-D6): (ppm) δ=6.1-6.0 (m, 2H), 4.9 (m, 2H), 3.7-3.5 (m, 5H),3.1-2.9 (m, 2H), 1.8-1.5 (m, 2H)

Preparation of Intermediate 3

Intermediate 2 (181 g, 0.5 mol) and triphenylsulfonium bromide (172 g,0.5 mol) were introduced to a H₂O:dichloro-methane=1:1 solution (1 L),and reacted for 12 hours at room temperature (25° C.). After thereaction was finished, the organic layer was washed 3 times with H₂O (1L), and then diethyl ether was introduced thereto to form precipitates.The precipitates were filtered and then dried to obtain Intermediate 3(compound B1) (280 g, 93%).

1H-NMR (DMSO-D6): (ppm) δ=7.4-7.1 (m, 15H), 6.1-6.0 (m, 2H), 4.5 (m,2H), 3.7-3.5 (m, 5H), 3.1-2.9 (m, 2H), 1.8-1.5 (m, 2H)

Preparation of Intermediate 4

Intermediate 1 (196.0 g, 1.0 mol), cyclopentadiene (132.2 g, 2.0 mol)and 4-methoxyphenol (2.4 g, 0.02 mol) were introduced to a high pressurereactor, reacted for 18 hours at 180° C., and then vacuum distilled toobtain Intermediate 4 (250 g, 95%).

1H-NMR (DMSO-D6): (ppm) δ=6.1-6.0 (m, 2H), 3.6 (s, 3H), 2.8 (m, H),2.6-2.4 (m, 3H), 2.2-1.6 (m, 4H), 1.2 (m, 2H), 1.0-0.7 (m, 2H)

Preparation of Intermediate 5

Intermediate 4 (131.0 g, 0.5 mol), sodium1,1-difluoro-2-hydroxyethane-1-sulfonate (110.5 g, 0.6 mol) and H₂SO₄(9.8 g, 0.1 mol) were introduced and reacted for 6 hours at 60° C. Afterthe reaction was finished, H₂O (1 L) was introduced thereto, the resultwas extracted 3 times with ethyl acetate (1 L), and the solvent wasremoved. The obtained result was recrystallized with EtOH to obtainIntermediate 5 (196.9 g, 92%).

1H-NMR (DMSO-D6): (ppm) δ=6.1-6.0 (m, 2H), 4.9 (dd, 2H), 3.7 (s, 3H),2.85 (m, H), 2.6-2.4 (m, 3H), 2.2-1.6 (m, 4H), 1.2 (m, 2H), 1.1-0.7 (m,2H)

Preparation of Intermediate 6

Intermediate 5 (214.0 g, 0.5 mol) and triphenylsulfonium bromide (172 g,0.5 mol) were introduced to a H₂O:dichloro-methane=1:1 solution (1 L),and reacted for 12 hours at room temperature (25° C.). After thereaction was finished, the organic layer was washed 3 times with H₂O (1L), and then diethyl ether was introduced thereto to form precipitates.The precipitates were filtered and then dried to obtain Intermediate 6(compound B2) (314.0 g, 94%).

1H-NMR (DMSO-D6): (ppm) δ=7.4-7.1 (m, 15H), 6.2-6.0 (m, 2H), 4.9 (dd,2H), 3.7 (s, 3H), 2.85 (m, H), 2.6-2.4 (m, 3H), 2.2-1.6 (m, 4H), 1.2 (m,2H), 1.1-0.7 (m, 2H)

Specific syntheses of Preparation Example 1 to Preparation Example 6described in Table 1 are as follows.

Preparation Example 1

1,2,4,5-Tetrazine (4.5 g, 0.055 mol) and Intermediate 3 (30 g, 0.05 mol)were introduced to dichloromethane (1 L), and the result was reacted for12 hours at room temperature. After the reaction was finished, diethylether was introduced thereto to form precipitates, and the precipitateswere filtered and then dried to obtain A1 (31.2 g, 95%).

1H-NMR (DMSO-D6): (ppm) δ=7.5 (d, H), 7.4-7.1 (m, 15H), 5.7 (s, H), 4.5(m, 2H), 3.7 (s, 3H), 3.1-2.8 (m, 3H), 2.3-2.2 (m, H), 2.1-2.0 (m, H),1.7-1.4 (m, 2H)

Preparation Example 2

3-Methyl-1,2,4,5-tetrazine (5.2 g, 0.055 mol) and Intermediate 3 (30 g,0.05 mol) were introduced to dichloromethane (1 L), and the result wasreacted for 12 hours at room temperature (25° C.). After the reactionwas finished, diethyl ether was introduced thereto to form precipitates,and the precipitates were filtered and then dried to obtain A2 (31.2 g,93%).

1H-NMR (DMSO-D6): (ppm) δ=7.4-7.1 (m, 15H), 5.6 (s, H), 4.4 (m, 2H), 3.7(s, 3H), 3.1-2.8 (m, 3H), 2.4-1.9 (m, 5H), 1.7-1.4 (m, 2H)

Preparation Example 3

3-Phenyl-1,2,4,5-tetrazine (8.7 g, 0.055 mol) and Intermediate 3 (30 g,0.05 mol) were introduced to dichloromethane (1 L), and the result wasreacted for 12 hours at room temperature (25° C.). After the reactionwas finished, diethyl ether was introduced thereto to form precipitates,and the precipitates were filtered and then dried to obtain A3 (34.4 g,94%).

1H-NMR (DMSO-D6): (ppm) δ=7.9 (m, 2H), 7.5-7.1 (m, 18H), 5.6 (s, H), 4.4(m, 2H), 3.7 (s, 3H), 3.1-2.8 (m, 3H), 2.2-1.9 (m, 2H), 1.7-1.4 (m, 2H)

Preparation Example 4

3,6-Dimethyl-1,2,4,5-tetrazine (6.1 g, 0.055 mol) and Intermediate 3 (30g, 0.05 mol) were introduced to dichloromethane (1 L), and the resultwas reacted for 12 hours at room temperature (25° C.). After thereaction was finished, diethyl ether was introduced thereto to formprecipitates, and the precipitates were filtered and then dried toobtain A4 (31.8 g, 94%).

1H-NMR (DMSO-D6): (ppm) δ=7.4-7.1 (m, 15H), 4.4 (m, 2H), 3.7 (s, 3H),3.2-2.8 (m, 3H), 2.5-1.9 (m, 8H), 1.7-1.4 (m, 2H)

Preparation Example 5

Methyl 4-(6-methyl-1,2,4,5-tetrazin-3-yl)benzoate (12.7 g, 0.055 mol)and Intermediate 3 (30 g, 0.05 mol) were introduced to dichloromethane(1 L), and the result was reacted for 12 hours at mom temperature (25°C.). After the reaction was finished, diethyl ether was introducedthereto to form precipitates, and the precipitates were filtered andthen dried to obtain A5 (36.2 g, 90%).

1H-NMR (DMSO-D6): (ppm) δ=7.4-7.1 (m, 19H), 4.4 (m, 2H), 3.9 (s, 3H),3.7 (s, 3H), 3.2-2.8 (m, 3H), 2.5-1.9 (m, 5H), 1.7-1.4 (m, 2H)

Preparation Example 6

3-Phenyl-6-(pyridin-2-yl)-1,2,4,5-tetrazine (12.9 g, 0.055 mol) andIntermediate 3 (30 g, 0.05 mol) were introduced to dichloro-methane (1L), and the result was reacted for 12 hours at room temperature (25°C.). After the reaction was finished, diethyl ether was introducedthereto to form precipitates, and the precipitates were filtered andthen dried to obtain A6 (36.9 g, 91%).

1H-NMR (DMSO-D6): (ppm) δ=8.5 (d, H), 7.9 (m, 2H), 7.4-7.1 (m, 21H), 4.4(m, 2H), 3.7 (s, 3H), 3.1-2.8 (m, 3H), 2.2-1.9 (m, 2H), 1.7-1.4 (m, 2H)

Synthesis of Resin Polymer R1

Composition A:B:C:D=50:20:20:10 Mw 6,000

2-methoxyethyl methacrylate (72 g, 0.5 mol), 2-methyl-2-adamantylmethacrylate (46.8 g, 0.2 mol), tert-butyl methacrylate (28.4 g, 0.2mol), methacrylic acid (8.6 g, 0.1 mol) and tetrahydrofuran (THF) (150g) were introduced to a flask, and stirred for 20 minutes under thenitrogen atmosphere.

AIBN (11.5 g, 0.07 mol) was dissolved in THF (10 g) to prepare aninitiator solution. After heating the reaction solution to 65° C., theinitiator solution was introduced thereto, and the result was stirredfor 18 hours. After the reaction was finished, the reaction solution wasdiluted with acetone, and precipitates were formed using an excessamount of hexane. The precipitates were filtered, and then dried for 18hours in a 30° C. oven to collect a polymer. A weight average molecularweight of Polymer R1 measured using gel permeation chromatography (GPC)was 6,000 g/mol.

Polymer R2

Norbomene Monomer 1 (17.1 g, 0.06 mol), Norbomene Monomer 2 (11.5 g,0.04 mol) and anisole (28.6 g) was introduced to a flask, and stirredfor 20 minutes under the nitrogen atmosphere. A palladium catalyst wasdissolved in anisole (1 g) under the argon atmosphere to prepare apalladium catalyst solution. After heating the reaction solution to 80°C., the palladium catalyst solution was introduced thereto, and theresult was stirred for 18 hours. After the reaction was finished, thereaction solution was diluted with THF, and precipitates were formedusing an excess amount of hexane. The precipitates were filtered, andthen dried for 18 hours in a 30° C. oven to collect a polymer. A weightaverage molecular weight of Polymer R2 measured using gel permeationchromatography (GPC) was 5,000 g/mol.

Polymer R3

Composition A:B:C:D=50:20:20:10 Mw 6,500

Polymerization was conducted in the same manner as with Polymer R1. Aweight average molecular weight of Polymer R3 measured using gelpermeation chromatography (GPC) was 6,500 g/mol.

Polymer R4

Composition A:B:C=60:30:10 Mw 5,500

Polymerization was conducted in the same manner as with Polymer R2. Aweight average molecular weight of Polymer R4 measured using gelpermeation chromatography (GPC) was 5,500 g/mol.

With each of the compounds and the polymers according to PreparationExamples 1 to 6, a photoresist composition comprising a content and amaterial of the following Table 2 was prepared.

TABLE 2 Photoacid Dose Generator Quencher Compound mJ/c LWR Resin (Mass%) (Mass %) (Mass %) m² Evaluation nm Evaluation Example 1 R1 R3 5.0 0.5A1 0.5  75 Δ  7.7 ○ (60%) (40%) Example 2 R1 R3 5.0 0.5 A3 0.5  64 ○ 8.3 ○ (60%) (40%) Example 3 R1 R4 5.0 0.5 A2 0.5  58 ○  8.4 ○ (60%)(40%) Example 4 R1 R4 5.0 0.5 A4 0.5  52 ○  8.0 ○ (60%) (40%) Example 5R2 R3 2.0 0.5 A1 0.5  47 ⊚  8.1 ○ (60%) (40%) Example 6 R2 R4 2.0 0.5 A40.5  44 ⊚  6.5 ⊚ (60%) (40%) Comparative R1 R3 5.0 1.0 — 112 X 13.8 XExample 1 (60%) (40%) Comparative R1 R4 5.0 1.0 —  98 X 11.5 Δ Example 2(60%) (40%) Comparative R2 R3 2.0 1.0 —  78 Δ  9.2 ○ Example 3 (60%)(40%) Comparative R2 R4 2.0 1.0 —  81 Δ  8.6 ○ Example 4 (60%) (40%)Comparative R1 R3 2.0 1.0 B1 0.5  73 Δ  8.2 ○ Example 5 (60%) (40%)Comparative R1 R3 2.0 1.0 B2 0.5  76 Δ 10.2 ○ Example 6 (60%) (40%)

In Table 2, the mass % of the photoacid generator, the quencher and thecompound are based on 4% of the total resin solid content.

In Table 2, the photoresist evaluation condition was 120° C./60 s forSOB, 110° C./90 s for PEB, and 50 nm to 60 nm for the photoresist layerthickness.

Optimum exposure (dose): based on 32 nm pitch, it was described as 50mJ/cm² or less (⊚), 70 mJ/cm² or less (◯), 90 mJ/cm² or less (Δ), andgreater than 90 mJ/cm² (X).

LWR (line width roughness): it was described as 7 nm or less (⊚), 10 nmor less (◯), 13 nm or less (Δ), and greater than 13 nm (X).

As seen from Table 2, it was identified that the compound according toone embodiment of the present application was capable of, by having thestructure of Chemical Formula 1, further enhancing contrast of anexposed portion and an unexposed portion in the photoresist processafterward, and was also capable of improving line width roughness (LWR)without reducing sensitivity.

According to Table 2, it was seen that Examples 1 to 6 were more usefulfor micropattern preparation compared to Comparative Examples 1 to 6 dueto low dose. This is due to the fact that the photoresist compositionused a photo-degradable base represented by Chemical Formula 1 having nosensitivity decrease caused by an increase in the base concentration,and as a result, a high resolution pattern was able to be obtained evenwith small exposure by having higher sensitivity compared to existingphotoresist compositions.

In addition, according to Table 2, it was seen that Examples 1 to 6 weremore useful for micropattern preparation compared to ComparativeExamples 1 to 6 due to low line width roughness (LWR). It was due tohigh compatibility of the photo-degradable base, and it was identifiedthat the compound was uniformly distributed into the photoresistcomposition improving LWR.

Furthermore, as seen in Examples 1 to 6, the compound according to oneembodiment of the present application comprises a compound having SO₃ ⁻and S⁺ ionic groups, and the photoresist layer was not able to be formedwhen the compound was not included since the function as a photoacidgenerator was not fulfilled.

1. A compound represented by Chemical Formula 1:

wherein, in the Chemical Formula 1, R₁ and R₂ are the same as ordifferent from each other, and each independently hydrogen; a halogengroup; a nitrile group; a hydroxyl group; an ester group; a substitutedor unsubstituted alkyl group; a substituted or unsubstituted aryl group;or a substituted or unsubstituted heteroaryl group; R₃ to R₆ are thesame as or different from each other, and each independently hydrogen; asubstituted or unsubstituted alkyl group; a substituted or unsubstitutedcycloalkyl group; a substituted or unsubstituted alkoxy group; asubstituted or unsubstituted silyl group; a substituted or unsubstitutedboron group; a substituted or unsubstituted amine group; a substitutedor unsubstituted arylphosphine group; a substituted or unsubstitutedphosphine oxide group; a substituted or unsubstituted aryl group; or asubstituted or unsubstituted heteroaryl group; and Ar₁ and Ar₂ are thesame as or different from each other, and each independently hydrogen; ahalogen group; a substituted or unsubstituted alkyl group; or asubstituted or unsubstituted aryl group.
 2. The compound of claim 1,wherein R₁ and R₂ are the same as or different from each other, and eachindependently hydrogen; a halogen group; an ester group; a substitutedor unsubstituted C₁ to C₆₀ alkyl group; a substituted or unsubstitutedC₆ to C₆₀ aryl group; or a substituted or unsubstituted C₂ to C₆₀heteroaryl group.
 3. The compound of claim 1, wherein R₄ to R₆ are thesame as or different from each other, and each independently asubstituted or unsubstituted C₆ to C₆₀ aryl group.
 4. The compound ofclaim 1, wherein Ar₁ and Ar₂ are the same as or different from eachother, and each independently hydrogen; or a halogen group, and at leastone of Ar₁ and Ar₂ is a halogen group.
 5. The compound of claim 1,wherein R₃ is a substituted or unsubstituted C₁ to C₆₀ alkyl group. 6.The compound of claim 1, wherein the compound is represented by any oneof the following Chemical Formulae:


7. A photoresist composition comprising: a resin; the compound of claim1; a photoacid generator (PAG); an acid diffusion control agent; and aquencher.
 8. The photoresist composition of claim 7, wherein the resincomprises at least one resin selected from a (meth)acrylate-based resin;a norbornene resin; a styrene-based resin; and an epoxy resin.
 9. Thephotoresist composition of claim 7, comprising the compound in an amountof from 0.1 parts by weight to 20 parts by weight based on 100 parts byweight of the resin.
 10. The photoresist composition of claim 7,comprising the photoacid generator in an amount of from 0.1 parts byweight to 20 parts by weight based on 100 parts by weight of the resin.11. The photoresist composition of claim 7, comprising the aciddiffusion control agent in an amount of from 0.1 parts by weight to 20parts by weight based on 100 parts by weight of the resin.
 12. Thephotoresist composition of claim 7, further comprising at least onematerial selected from a surfactant; a photosensitizer; and a photobasegenerator.
 13. A photoresist layer kozu comprising the photoresistcomposition of claim
 7. 14. A method for preparing a photoresistpattern, the method comprising: forming a photoresist layer by coatingthe photoresist composition of claim 7 on a semiconductor substrate;selectively exposing the photoresist layer to ultraviolet rays; anddeveloping the exposed photoresist layer in a developing solution. 15.The method for preparing a photoresist pattern of claim 14, wherein theselectively exposing of the photoresist layer is aligning a mask on thephotoresist layer, and exposing an area of the photoresist layer notcovered by the mask to the ultraviolet rays.
 16. The method forpreparing a photoresist pattern of claim 14, wherein the developing ofthe exposed photoresist layer is removing the exposed portion in thephotoresist layer by immersing in the developing solution.